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Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes

Nature Materials volume 21, pages 228–236 (2022)Cite this article

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Abstract

Zwitterionic materials can exhibit unique characteristics and are highly tunable by variation to the covalently bound cationic and anionic moieties. Despite the breadth of properties and potential uses reported to date, for electrolyte applications they have thus far primarily been used as additives or for making polymer gels. However, zwitterions offer intriguing promise as electrolyte matrix materials that are non-volatile and charged but non-migrating. Here we report a family of zwitterions that exhibit molecular disorder and plasticity, which allows their use as a solid-state conductive matrix. We have characterized the thermal, morphological and structural properties of these materials using techniques including differential scanning calorimetry, scanning electron microscopy, solid-state NMR and X-ray crystallography. We report the physical and transport properties of zwitterions combined with lithium salts and a lithium-functionalized polymer to form solid or high-salt-content liquid electrolytes. We demonstrate that the zwitterion-based electrolytes can allow high target ion transport and support stable lithium metal cell cycling. The ability to use disordered zwitterionic materials as electrolyte matrices for high target ion conduction, coupled with an extensive scope for varying the chemical and physical properties, has important implications for the future design of non-volatile materials that bridge the choice between traditional molecular and ionic solvent systems.

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Fig. 1: Characterization of the neat zwitterions.
Fig. 2: Thermal and transport properties of 10 mol% LiFSI in ZI(1).
Fig. 3: The performance of 10 mol% LiFSI in ZI(1) in lithium metal symmetrical and full cells.
Fig. 4: Conductivity, NMR and cell performance for the 10 mol% LiFSI in ZI(1) and its mixture with lithium-functionalized polymer NPs.
Fig. 5: Conductivity and symmetrical lithium cell performance of the liquid 50 mol% LiFSI in ZI(1) electrolyte.

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Data availability

The data represented in the figures in the main paper are available as data files. Source data are provided with this paper. Additional source data are available from the corresponding author upon reasonable request. The crystallographic information file for ZI(1) is available as a Supplementary Information file and has been deposited in the Cambridge Structural Database, Cambridge Crystallographic Data Centre deposition number 2103332.

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Acknowledgements

This work was supported by the Australian Research Council (ARC) through Discovery Grant DP170101087, the Centre of Excellence for Electromaterials Science (CE140100012) and the ARC Training Centre for Future Energy Storage Technologies (IC180100049). L.P. received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement no. 797295. D.M. acknowledges funding by the Basque Government through Elkartek KK-2020/00078 and Agencia Estatal de Investigación (PID2020-119026GB-I00).

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Authors and Affiliations

  1. Institute for Frontier Materials, Deakin University, ARC Centre of Excellence for Electromaterials Science, Waurn Ponds, Victoria, Australia

    Faezeh Makhlooghiazad, Luke A. O’Dell, Luca Porcarelli, Maria Forsyth & Jennifer M. Pringle

  2. Joxe Mari Korta Center, POLYMAT, University of the Basque Country, Donostia–San Sebastian, Spain

    Luca Porcarelli & David Mecerreyes

  3. School of Chemistry, Monash University, Clayton, Victoria, Australia

    Craig Forsyth

  4. Boron Molecular, Noble Park, Victoria, Australia

    Nurul Quazi, Mousa Asadi & Oliver Hutt

  5. Ikerbasque, Basque Foundation for Science, Bilbao, Spain

    David Mecerreyes

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Contributions

F.M. designed and executed the experiments, analysed data and prepared the manuscript. L.A.O. supervised NMR experiments, analysed data and edited the manuscript. L.P. designed and synthesized the NPs and analysed results. C.F. collected X-ray structure data and analysed and interpreted results. N.Q., M.A. and O.H. synthesized zwitterions, including the experimental design, execution and analysis of synthesis results. D.M. conceived and designed the lithium-functionalized polymer NPs. M.F. contributed to project planning, interpretation of results and manuscript editing. J.M.P. contributed to project concept and design, interpretation of results and manuscript preparation.

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Correspondence to Jennifer M. Pringle.

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Peer review information Nature Materials thanks Catalin Gainaru and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–19, Tables 1–4 and Discussion.

Supplementary Data

Crystallographic information file for ZI(1).

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Statistical source data.

Source Data Fig. 3

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Statistical source data.

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Makhlooghiazad, F., O’Dell, L.A., Porcarelli, L. et al. Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes. Nat. Mater. 21, 228–236 (2022). https://doi.org/10.1038/s41563-021-01130-z

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